The present invention relates to a novel water-repellent and oil-repellent perfluoro group-containing compound and a hardened polymer thereof.
The perfluoro group-containing compound is excellent in heat resistance because the linkages between carbon atoms and fluorine atoms are very strong and the compound has a low friction coefficient. For this reason, the perfluoro group-containing compound has been used for protecting the surface of a substrate by, for instance, applying it to the substrate surface; or incorporating it into a paint and applying the paint to the substrate surface to thus impart water repellency or oil repellency to the surface. For instance, Published International Patent Application No. WO98/12163 discloses a (meth)acrylic acid ester of perfluoro group-containing alcohol and a hardened polymer thereof and Japanese Patent Provisional Publication No. Hei 11-2702 discloses a low refractive index film comprising a perfluoro group-containing compound.
Under such circumstances, there has been desired for the development of a perfluoro group-containing compound and a hardened polymer thereof, whose adherence to the surface of a substrate is further improved.
Accordingly, it is an object of the present invention to provide a water-repellent and oil-repellent perfluoro group-containing novel, polymerizable compound.
It is another object of the present invention to provide a hardened polymer of the compound, whose adherence to the surface of a substrate is quite excellent.
The perfluoro group-containing compound of the present invention developed for accomplishing the foregoing objects is one represented by the following formula (I): 
In Formula (I), xe2x80x94Rfxe2x80x94 is a perfluoro group selected from the group consisting of xe2x80x94CH2xe2x80x94(CF2)mxe2x80x94(CH2)nxe2x80x94(wherein m is an integer ranging from 1 to 20 and n is also an integer ranging from 0 to 1), xe2x80x94CH2xe2x80x94(CF2)pxe2x80x94C[xe2x80x94(CF2)qxe2x80x94F][xe2x80x94(CF2)rxe2x80x94F]xe2x80x94CH2xe2x80x94 (wherein p is an integer ranging from 1 to 10, q is an integer ranging from 0 to 22 and r is an integer ranging from 1 to 22), xe2x80x94CH2xe2x80x94(CF2)sxe2x80x94(xe2x80x94Oxe2x80x94CtF2t)uxe2x80x94Oxe2x80x94(CF2)vxe2x80x94(CH2)wxe2x80x94 (wherein s, t, u, v and w are integers ranging from 1 to 3, 1 to 4, 1 to 100, 0 to 3 and 0 to 1, respectively), 
(wherein x1 and x2 each is an integer ranging from 0 to 10); xe2x80x94A represents xe2x80x94OH or a group: 
when n, v and w of the foregoing xe2x80x94Rfxe2x80x94 not 0, orxe2x80x94CyF2y+1 (y is an integer ranging from 1 to 22) when m=1xcx9c3 and n=1, m+y=6xcx9c22 and n=0, v=w=0, in the foregoing group: xe2x80x94Rfxe2x80x94, or xe2x80x94CzF2zxe2x88x921 (z is an integer ranging from 3 to 20) when m=1xcx9c10 and n=0, v=w=0 in the foregoing group: xe2x80x94Rfxe2x80x94.
The foregoing group: xe2x80x94CH2xe2x80x94(CF2)mxe2x80x94(CH2)nxe2x80x94may be, for instance, a dehydrogenated residue of 2,2-difluoropropane diol, 2,2,3,3-tetrafluorobutane diol, 2,2,3,3,4,4-hexafluoropentane diol, 2,2,3,3,4,4,5,5-octafluorohexane diol, 2,2,3,3,4,4,5,5,6,6-decafluoroheptane diol, 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluorooctane diol, 2,2,3,3,4,4,5,5,6,6,7,7,8,8-tetradecafluorononane diol or 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-heptadecafluorodecane diol, when n is not 0.
The foregoing group: xe2x80x94CH2xe2x80x94(CF2)pxe2x80x94C[xe2x80x94(CF2)qxe2x80x94F][xe2x80x94(CF2)rxe2x80x94F]xe2x80x94CH2xe2x80x94may be, for instance, a dehydrogenated residue of 2-fluoro-2-perfluorooctyl-1,3-propane diol, 2-fluoro-2-perfluoroisooctyl-1,3-propane diol or 2-fluoro-2-perfluoro (4-ethyl-hexyl)-2-hydroxymethyl-1-methanol.
The foregoing group: xe2x80x94CH2xe2x80x94(CF2)sxe2x80x94(xe2x80x94Oxe2x80x94CtF2t)uxe2x80x94Oxe2x80x94(CF2)vxe2x80x94(CH2)wxe2x80x94 may be, for instance, a dehydrogenated residue of 2,2,4,4-tetrafluorodiethylene glycol, 2,2,4,4,5,5,7,7-octafluorotriethylene glycol, 2,2,4,4,5,5,7,7,8,8,10,10-dodecafluorotetraethylene glycol, 2,2,4,4,5,5,7,7,8,8,10,10,11,11,13,13-heptadecafluoro pentaethylene glycol, 2,2,4,4,5,5,7,7,8,8,10,10,11,11,13,13,14,14,16,16-eicosafluorohexaethylene glycol, 2,2,4,4,5,5,7,7,8,8,10,10,11,11,13,13,14,14,16,16,17,17,19,19-tetracosafluoroheptaethylene glycol, 2,2,4,4,5,5,7,7,8,8,10,10,11,11,13,13,14,14,16,16,17,17,19,19,20,20,22,22-octacosafluorooctaethylene glycol, 2,2,4,4,5,5,7,7,8,8,10,10,11,11,13,13,14,14,16,16,17,17,19,19,20,20,22,22,23,23,25,25-dotriacontafluorononaethylene glycol, 2,4,4-trifluoro-2,5-di(trifluoromethyl)diethylene glycol, 2,4,4,5,7,7-hexafluoro-2,5,8-tri(trifluoromethyl)triethylene glycol, 2,4,4,5,7,7,8,10,10-nonafluoro-2,5,8,11-tetra(trifluoromethyl)tetraethylene glycol, 2,4,4,5,7,7,8,10,10,11,13,13-dodecafluoro-2,5,8,11,14-penta(trifluoromethyl)pentaethylene glycol, 2,4,4,5,7,7,8,10,10,11,13,13,14,16,16,17-pentadecafluoro-2,5,8,11,14,17-hexa(trifluoromethyl)hexaethylene glycol, 2,4,4,5,7,7,8,10,10,11,13,13,14,16,16,17,19,19,20-octadecafluoro-2,5,8,11,14,17,20-hepta(trifluoromethyl)heptaethylene glycol, 2,4,4,5,7,7,8,10,10,11,13,13,14,16,16,17,19,19,20,22,22,23-docosafluoro-2,5,8,11,14,17,20,23-octa-(trifluoromethyl) octaethylene glycol, 2,4,4,5,7,7,8,10,10,11,13,13,14,16,16,17,19,19,20,22,22,23,25,25,26-tetracosafluoro-2,5,8,11,14,17,20,23,26-nona(trifluoromethyl)nonaethylene glycol, 2,2,3,3,4,4,6,6,7,7,8,8-dodecafluoroditetramethylene glycol, 2,2,3,3,4,4,6,6,7,7,8,8,9,9,11,11,12,12,13,13-eicosafluorotritetramethylene glycol, 2,2,3,3,4,4,6,6,7,7,8,8,9,9,11,11,12,12,13,13,14,14,16,16,17,17,18,18-octacosafluorotetratetramethylene glycol, 2,2-bis(4-hydroxy-decafluorocyclohexyl)-1,3-hexafluoropropane, 2,2-bis (4-hydroxymethyl-decafluorocyclohexyl)-1,3-hexafluoropropane, 2,2-bis[4-oxy(1,1-difluoroethoxy)-decafluorocyclohexyl]-1,3-hexafluoropropane, or 2,2-bis[4-oxy(1-perfluoromethyl-1-fluoroethoxy)-decafluorocyclohexyl]-1,3-hexafluoropropane.
The group: (CyF2y+1)xe2x80x94CH2Oxe2x80x94 which constitutes the group: xe2x80x94(CyF2y+1), may be, for instance, a dehydrogenated residue of perfluoromethanol, perfluoroethyl methanol, perfluoropropyl methanol, perfluorobutyl methanol, perfluoropentyl methanol, perfluorohexyl methanol, perfluorooctyl methanol, perfluorononyl methanol, perfluorodecyl methanol, perfluoroundecyl methanol, perfluorododecyl methanol, perfluorotridecyl methanol, perfluorotetradecyl methanol, perfluoropentadecyl methanol, perfluorohexadecyl methanol, perfluoroheptadecyl methanol, perfluorooctadecyl methanol, perfluorononadecyl methanol, perfluoroeicosyl methanol, or perfluoroheneicosyl methanol. In addition, the group: (CyF2y+1)xe2x80x94OCF2CH2Oxe2x80x94 may be, for instance, a dehydrogenated residue of 2-perfluoromethoxy-2,2-difluoroethanol, 2-perfluoroethoxy-2,2-difluoroethanol. The group: (CyF2y+1)xe2x80x94(CF2CF2xe2x80x94Oxe2x80x94)uxe2x80x94CF2CH2Oxe2x80x94 may be, for instance, a dehydrogenated residue of 2-perfluorobutoxy-2,2-difluoroethanol, 2-perfluorooctoxy-2,2-difluoroethanol, 5-perfluoromethoxy-4,4,5,5-tetrafluoroethoxy-2,2-difluoroethanol, 5-perfluorobutoxy-4,4,5,5-tetrafluoroethoxy-2,2-difluoroethanol, 5-perfluorooctoxy-4,4,5,5-tetrafluoroethoxy-2,2-difluoroethanol, 8-perfluoromethoxy-7,7,8,8-tetrafluoroethoxy-4,4,5,5-tetrafluoroethoxy-2,2-difluoroethanol, 8-perfluorooctoxy-7,7,8,8-tetrafluoroethoxy-4,4,5,5-tetrafluoroethoxy-2,2-difluoro-ethanol, 11-perfluoromethoxy-10,10,11,11-tetrafluoroethoxy-7,7,8,8-tetrafluoroethoxy-4,4,5,5-tetrafluoroethoxy-2,2-difluoroethanol, or 11-perfluorooctoxy-10,10,11,11-tetrafIuoroethoxy-7,7,8,8-tetrafluoroethoxy-4,4,5,5-tetrafluoroethoxy-2,2-difluoroethanol.
Examples of the group: (CzF2zxe2x88x921)xe2x80x94CH2Oxe2x80x94 which constitutes the group: xe2x80x94(CzF2zxe2x88x921)xe2x80x94 may be, for instance, a dehydrogenated residue of 1-undecafluorocyclohexyl methanol, 2-fluoro-2-undecafluorocyclohexyl ethanol, or 2,2,3-trifluoro-3-undecafluorocyclohexyl propanol.
A method for preparing a perfluoro group-containing epoxy compound represented by the foregoing formula (I) comprises the step of reacting a perfluoro group-containing mono- or di-alcohol with a halogenated epoxy propyl.
The perfluoro group-containing alcohol as a starting material can be prepared by, for instance, fluorinating a diester of an alkyl diol with fluorine gas in 1,1,2-trichloro-trifluoroethane and then reducing the fluorinated product with lithium aluminum hydride. The procedures for preparing the perfluoro group-containing alcohol will be described below while taking a di-alcohol (1) represented by the formula: HOxe2x80x94CH2xe2x80x94Rfxe2x80x94CH2xe2x80x94OH as an example of such an alcohol. As will be seen from the following reaction scheme (V): 
the alcohol reacts with a halogenated epoxy propyl (2) in the presence of a basic reagent to give a perfluoro group-containing epoxy compound (3). In this respect, the basic reagent may be, for instance, a metal hydroxide such as sodium hydroxide, potassium hydroxide, lithium hydroxide or calcium hydroxide; a metal alcoholate such as sodium methylate or potassium methylate; hydroxylamine; or tetraalkyl ammonium salt.
Alternatively, the perfluoro group-containing epoxy compound may likewise be prepared by reacting a perfluoro group-containing mono- or di-alcohol with a halogenated allyl and then oxidizing the reaction product with a peracid. Examples of such peracids are performic acid, peracetic acid, perpropionic acid, perbutyric acid, persuccinic acid, peradipic acid, pertrifluoroacetic acid, perbenzoic acid, monoperoxyphthalic acid, and p-nitro-perbenzoic acid.
The hardened polymer of the present invention is one obtained by polymerizing the perfluoro group-containing epoxy compound represented by the foregoing formula (I) using an amine, an acid anhydride, a polyamide resin, an imidazole, a mercaptan, a phenol, a Lewis acid-amine complex, or a photo-setting agent. Heating or irradiation with light rays can initiate the polymerization.
Examples of such amines are linear aliphatic polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine and diethylaminopropylamine; alicyclic polyamines such as N-aminoethyl piperazine and isophorone-diamine; aromatic polyamines such as xylylene-diamine, diamino-diphenyl methane and diamino-diphenyl sulfone; ethylene oxide or propylene oxide adducts of these polyamines; and modified amines such as cyanoethyl-modified polydmines and ketimine.
Examples of the foregoing acid anhydrides-are aromatic acid anhydrides such as phthalic anhydride, trimellitic anhydride and pyromellitic anhydride; and anhydrides of aliphatic acids such as maleic anhydride, succinic.anhydride, tetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, methyl nadic anhydride, alkenyl succinic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride and methyl-cyclohexene tetracarboxylic anhydride.
Examples of the foregoing polyamide resins are reaction products of dimeric acids or polycarboxylic acids with polyamines. Examples of the foregoing imidazoles are 2-methyl imidazole, 2-ethyl-4-methyl imidazole, 2-phenyl imidazole and combinations thereof with dicyan diamides. The foregoing mercaptans may be, for instance, liquid polymercaptans and polysulfide resins. Examples of phenols are novolak phenol, cresol novolak phenol and polyvinyl phenol.
Moreover, examples of the foregoing Lewis acid-amine complexes are complexes of Lewis acids such as boron trifluoride, phosphorus pentafluoride, arsenic pentafluoride and antimony pentafluoride with amines such as monoethylamine, benzylamine, piperidine, triethylamine and aniline. Examples of the foregoing photo-setting agents are aromatic diazonium Lewis acid salt, diallyl iodonium Lewis acid salt, triallylsulfonium Lewis acid salt and triallyl selenide.
The foregoing compounds can likewise be polymerized using other catalysts such as dicyan diamide, organic acid hydrazides, diaminomaleonitrile and derivatives thereof, melamine and derivatives thereof, amine imide and polyamine salts. Moreover, the catalyst may be those listed above absorbed on molecular sieve or encapsulated products of the foregoing catalysts. These catalysts may be used alone or in any combination.
The prepolymer according to the present invention is one obtained by the reaction of a perfluoro group-containing epoxy compound represented by the foregoing formula (I) with at least one member selected from the group consisting of amines, diols, dicarboxylic acids, acid anhydrides, polyamide resins, imidazoles, mercaptans, phenols, and Lewis acid-amine complexes and has a number average molecular weight ranging from 0.5xc3x97103 to 1xc3x97106.
Examples of amines, acid anhydrides, polyamides, imidazoles, mercaptans, phenols, and Lewis acid-amine complexes are the same as those listed above; examples of diols are alkyl diols and perfluoro group-containing dialcohols. Examples of dicarboxylic acids are the foregoing aromatic acids and aliphatic acids. It is also possible to use dicyan diamides, organic acid hydrazides, diaminomaleonitriles and derivatives thereof, melamine and derivatives thereof, amine imides, polyamine salts, or those listed above absorbed on molecular-sieve or encapsulated products of the foregoing catalysts.
The hardened polymers other than those listed above include the foregoing prepolymers, which are crosslinked with crosslinking agents such as polyisocyanates or acid anhydrides.
More specifically, hydroxyl groups are newly formed through the addition reaction of the epoxy groups of the perfluoro group-containing epoxy compound and diamines. These hydroxyl groups undergo addition reactions with the isocyanate groups of polyisocyanates to cause polymerization with crosslinking in a network structure and to thus cause hardening.
Examples of polyisocyanates are diisocyanates and triisocyanates such as toluene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, triphenylene triisocyanate, tris(isocyanate phenyl)thiophosphate, hexamethylene diisocyanate, methylene-bis(cyclohexyl diisocyanate), isophorone diisocyanate, trimethyl hexamethylene diisocyanate, bis(isocyanate methyl)cyclohexane and norbornene diisocyanate; adducts, buretes and isocyanurates derived from the foregoing diisocyanates, and block derivatives in which the isocyanate groups are protected with, for instance, phenols in order to impart storage stability to diisocyanates and which are dissociated into those carrying free isocyanate groups by heating prior to use.
The perfluoro group-containing polymerizable compounds of the present invention are those represented by the following formula (II):
xe2x80x83R1xe2x80x94Oxe2x80x94CH2xe2x80x94CH(OH)xe2x80x94CH2xe2x80x94Oxe2x80x94Rfxe2x80x94Bxe2x80x83xe2x80x83(II)
In Formula (II), xe2x80x94Rfxe2x80x94 is the same as that defined above in connection with Formula (I); xe2x80x94B is xe2x80x94OH or xe2x80x94Oxe2x80x94CH2CH(OH)xe2x80x94CH2xe2x80x94Oxe2x80x94R2, or xe2x80x94CyF2y+1 or xe2x80x94CzF2zxe2x88x921 (y and z are the same as those defined above); R1 and R2 each is a dehydroxyl residue of a (meth)acryloyl group-containing compound or a vinyl group-containing compound.
The perfluoro group-containing polymerizable compound represented by Formula (II) can be prepared by reacting the epoxy group of a perfluoro group-containing epoxy compound with the hydroxyl group of a (meth)acryloyl group-containing compound or a vinyl group-containing compound through the ring-opening addition reaction.
A specific example thereof will be described below while taking the reaction of a perfluoro group-containing epoxy compound (3) with acrylic acid (4) as a typical example. The reaction is shown in the following reaction scheme (VI): 
As will be seen from the reaction scheme (VI), the carboxyl group of the acrylic acid (4) is reacted with the epoxy group of the compound (3) through the ring-opening addition reaction in the presence of a basic reagent to give an acrylic acid diester (5). The basic reagent may be, for instance, tertiary amines such as dimethyl benzylamine; quaternary ammonium salts such as tetramethylammonium chloride; or phosphorus atom-containing compounds such as triphenyl phosphine.
Examples of (meth)acryloyl group-containing compounds include (meth)acrylic acid, (meth)acryloyloxy aliphatic acids, such as (meth)acryloyloxy propionic acid. These (meth)acryloyl group-containing compounds are reacted with epoxy compounds (3) through the ring-opening addition reaction to give polymerizable ester compounds.
Examples of vinyl group-containing compounds are allyl alcohol, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether and monovinyl ether of cyclohexane dimethanol. These vinyl group-containing compounds are reacted with epoxy compounds (3) through the ring-opening addition reaction in the presence of a catalyst to form ether bonds and to thus give polymerizable compounds. As such catalysts, there may be listed, for instance, metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide and calcium hydroxide; metal alcoholates such as sodium methylate and potassium methylate; and boron trifluoride-ether complexes.
Alternatively, it is also possible to use acrylic acid monoesters such as those prepared by reacting halogenated epoxypropyl with only one terminal hydroxyl group of the dialcohol (1) or by reacting halogenated epoxypropyl with the hydroxyl group of a monoalcohol to give a monoether and then reacting the monoether with (meth)acryloyl group-containing compounds. It is also possible to use those obtained by reacting the monoether with vinyl group-containing compounds.
Prepolymers of the present invention other than those described above are ones formed by the polymerization of the unsaturated groups of the perfluoro group-containing compounds represented by the foregoing Formula (II) and having a number average molecular weight ranging from 0.5xc3x97103 to 1xc3x97106. The perfluoro group-containing polymerizable compound can be polymerized under the irradiation of light rays or in the presence of a heat polymerization initiator to give a prepolymer.
Another hardened polymer according to the present invention is one obtained by crosslinking the foregoing prepolymer with a crosslinking agent such as a polyisocyanate or an acid anhydride. Examples of such polyisocyanates or acid anhydrides usable herein are the same as those already listed above. The hardened polymer may likewise be one obtained by polymerization, with crosslinking, of the prepolymer through the unsaturated groups thereof.
More specifically, the hardened polymer may be prepared as follows: A perfluoro group-containing compound is reacted with a dialcohol to form a prepolymer. Then a solution containing the prepolymer and a diisocyanate is prepared, followed by applying the solution onto the surface of a substrate such as plastics, metals, wood, paper, glass and concrete, and then heating the resulting film or irradiating it with visible light rays or ultraviolet rays. The unsaturated groups present in the polymerizable compounds are polymerized with crosslinking and thus hardened in a network structure to thus form a hardened polymer.
Alternatively, such a coated film may be those obtained by applying a polymerizable compound-containing paint or ink onto the surface of such a substrate.
The perfluoro groups present in the hardened polymer are linked to unsaturated groups through ether bonds originated from epoxy propyl ether and therefore, they have high degree of freedom and a high migration ability. The perfluoro groups does not inhibit the exposure, on the molecular surface, of polar groups such as hydroxyl, ether and ester groups generated through the opening of the epoxy rings. For this reason, when the perfluoro group-containing polymerizable compound is polymerized on the surface of a substrate, the hardened polymer shows excellent adhesion to the interface of a substrate through the interaction between the polar groups of the polymer and those present on the surface. If the perfluoro group has a ring-like structure or it is in a branched state, the degree of its freedom is further enhanced and therefore, the adhesion between the polymer and the substrate is in turn further improved.
These hardened polymers are firmly adhered to the substrate surface and therefore, they are not easily separated from the surface. Moreover, the perfluoro groups of the polymer are exposed on the surface to thus reduce the interface energy of the substrate and accordingly, the surface of the substrate is excellent in the water-repellency and oil-repellency. The hardened polymer may be used as a coated film for protecting the substrate and/or an antireflecting film for the substrate.
The present invention will be described in more detail below with reference to the following Examples, but the present invention is not restricted to these specific Examples at all.
Specifically, the perfluoro group-containing epoxy compound and the hardened polymer thereof according to the present invention can be prepared according to the following methods.